Decoupling Catalysis and Chain-Growth Functions of Mono(μ-alkoxo

Aug 9, 2018 - Jennifer Imbrogno†§ , Robert C. Ferrier, Jr.† , Bill K. Wheatle† , Michael J. Rose‡ , and Nathaniel A. Lynd*†§. †McKetta D...
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Decoupling catalysis and chain-growth functions of mono(µ-alkoxo)-di(alkylaluminum)s in epoxide polymerization: Emergence of the N/Al adduct catalyst Jennifer Imbrogno, Robert Charles Ferrier Jr., Bill Kristoff Wheatle, Michael J. Rose, and Nathaniel A. Lynd ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.8b02446 • Publication Date (Web): 09 Aug 2018 Downloaded from http://pubs.acs.org on August 12, 2018

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is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

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Decoupling Catalysis and Chain-Growth Functions of Mono(µ-alkoxo)-di(alkylaluminum)s in Epoxide Polymerization: Emergence of the N/Al Adduct Catalyst Jennifer Imbrogno, †,§, Robert C. Ferrier, Jr.†¶, Bill K. Wheatle†, Michael J. Rose‡, Nathaniel A. Lynd†,§,* †

McKetta Department of Chemical Engineering, and the ‡Department of Chemistry, §Center for

Dynamics and Control of Materials, The University of Texas at Austin, Austin, TX, 78712, USA

ABSTRACT. A mono(µ-oxo)-dialkylaluminum (MOD) catalyst and initiator for epoxide polymerization, [(H3C)2NCH2CH2(µ2-O)Al(iBu)2∙Al(iBu)3] (1), produced a ca. 170 fold enhancement in epoxide polymerization rate over previously reported MOD initiators demonstrated with allyl glycidyl ether (AGE). This discovery reduces polymerization times to minutes. (1) exhibited an exponential dependence of polymerization rate on concentration, rather than an expected low integer order relationship. A proposed polymerization intermediate was identified via direct synthesis, isolation, kinetic comparison, and corroborating in situ spectroscopic evidence to be a symmetric bis(µ-alkoxo-dialkylaluminum) (BOD) with a characteristic R3N-AlRʹ3 (N-Al) adduct. The N-Al adduct on the BOD intermediate is proposed to act as catalyst, whereas the aluminoxane ring is proposed to be the site of monomer enchainment based on mass spectrometry and spectroscopic analysis of resultant polymer

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structure. The distinct catalytic and initiation/propagation functionalities were separated into separate species and the catalytic activity of the N-Al adduct was demonstrated in the presence of a distinct aluminoxane initiator. Each equivalent of N-Al adduct relative to initiator resulted in an abrupt (ca. 5–10 fold) increase in the polymerization rate of AGE. The resultant N-Al adduct catalyst represents aversatile tool for rapid functional macromolecular synthesis.

Keywords: Aluminum, Lewis pair, N-Al adduct, polyether, polymerization catalysis Introduction Epoxide-based polyethers enable compositional control of structure-property relationships in a macromolecular platform due to the wide variety of available monomers and the relatively indiscriminate ring-strain driving force for polymerization.1,2 In spite of the versatility offered by epoxides as monomers, no general-use, consensus technique for epoxide polymerization for nonspecialists has emerged in common usage in the same sense that it has for many other monomer classes such as vinyls,3 cyclic olefins,4,5 and lactones.6-9 While anionic ring-opening polymerization (AROP) has served as the de facto consensus polymerization technique for epoxides, only lower molecular weights are generally obtainable for any epoxide except for the simplest case, ethylene oxide.10-12 The performance of AROP is sensitive to, and varies widely with monomer structure,13 and chain-transfer-to-monomer limits control of chain-end functionality and control of molecular weight in many systems.12 Numerous catalytic strategies for epoxide polymerization have been reported to provide access to high14 and controlled molecular weight materials possessing narrow dispersities,15,16,17 and controlled stereochemistry.14,18-23 These valuable contributions have expanded mechanistic understanding of epoxide polymerization and provided synthetic access to novel materials. Our work focuses on establishing a polymerization method that is easy to use, based on Earth-

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abundant metals such as aluminum,24-28 characteristically “living”29-34 and provides control of chain-end functionality,35,36 and functional group tolerance.37 Recently reported mono(µ-alkoxo)-di(alkylaluminum) (MOD) compounds combine many of the advantages of the catalytic approaches (i.e., tolerance of monomer functionality) and exhibit a degree of control to epoxide polymerizations consistent with living controlled polymerization with neither auto-termination nor chain transfer with associated control of molecular weight via the polymerization stoichiometry. The MOD initiators are trivial to synthesize and use, and under controlled conditions provide stoichiometric control over molecular weight, end-group structure, versatility in monomer substrates, and macromolecular architecture.37,38 Scheme 1 shows the molecular structure of the MOD initiator (1) utilized in this work and general polymerization scheme.

Scheme

1.

O)Al(iBu)2∙Al(iBu)3

Mono(µ-oxo)-di(alkylaluminum) (1) initiators

(MOD)

are effective for general

[(Me)2NCH2CH2(µ2and

rapid

epoxide

polymerization. In the original report of MOD initiator synthesis and activity for polymerization, [(Bn)2NCH2CH22(µ2-O)Al(Et)2∙Al(Et)3] (2) required days for complete consumption of monomer.38 We later investigated the effect of simple alkylaluminum substitution, which led to a four-fold increase in polymerization rate.37 In this report, we observed an unexpected and substantial increase in polymerization rate of ca. 100 fold over our originally-reported MOD initiator via a change in alkylamine substitution. The polymerization rate was found to depend unusually strongly on MOD (1) concentration. These results were obtained with

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[(Me)2NCH2CH2(µ2-O)Al(iBu)2∙Al(iBu)3] (1) shown in Scheme 1 and Figure 1, which required only minutes for complete consumption of allyl glycidyl ether (AGE) to 10,000 g/mol poly(allyl glycidyl ether) (PAGE). The dramatic increase in rate associated with a relatively simple structural change of the initiator prompted us to further explore the mechanistic aspects of MODinitiated polymerizations with isolation of a potential polymerization intermediate that was substantiated upon further investigation. The intermediate was characterized as the product of MOD dimerization with migration of the datively-bound trialkylaluminum to the amine. This transformation yielded a symmetric bis(µ-alkoxo-dialkylaluminum) (BOD) with the aluminum alkoxide serving as the site of monomer enchainment and the R3N-AlRʹ3 moiety serving as catalyst. The enchainment and catalytic functionalities were ultimately decoupled into distinct chemical entities creating a new, two-component, versatile platform for functional epoxide polymerization. Results and Discussion Remarkable

polymerization

rate

increase

with

(1)

[(H3C)2NCH2CH2(µ2-

O)Al(iBu)2∙Al(iBu)3] relative to homologous mono(µ-alkoxo)-di(alkylaluminum) species (2)–(4).

A

new

MOD

initiator

was

synthesized

from

dimethylamino-ethanol

and

triisobutylaluminum resulting in (1), which was crystallized directly from the reaction medium and characterized by X-ray crystallography (structure shown in Figure 1a) and NMR spectroscopy as shown in Supporting Information (SI), Figures S1, S9, and Tables S1–S6. Previously published MOD structures as synthesized from dibenzyl-amino-ethanol and triethyl (2), trimethyl (3) and triisobutyl aluminum (4) are also shown in Figure 1a.37,38 As with other MOD structures, the new [(Me)2NCH2CH2(µ2-O)Al(iBu)2∙Al(iBu)3 (1) exhibited strong structure-kinetic relationships for epoxide polymerization.

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Neat polymerizations were conducted to compare the rates among new (1) and previously reported homologous MOD initiators (2)–(4). The monomer-to-initiator ratio was selected to create a 10,000 g/mol poly(allyl glycidyl ether) (PAGE) at 100% conversion of allyl glycidyl ether (AGE): [AGE]0/[MOD]0 = 87. The polymerization using (1) was complete after ca. 20 minutes and produced a large exotherm presumably from the rapid release of epoxide ring strain energy (ca. 25 kcal/mol),39 raising the unbuffered reaction temperature of the polymerization to ca. 80 ºC as measured by the in-situ ReactIR 15 FTIR probe. The conversion of AGE, as determined by 1H NMR spectroscopy of the crude reaction mixture, was quantitative and the number-average molecular weight (Mn), determined by size exclusion chromatography (SEC) with refractive index, viscometer, and light scattering detection, was 9,400 g/mol with a molecular weight dispersity (Đ) of 1.15. To quantitatively compare rates of polymerization, we report apparent rate constants (kapp [=] s–1) by fitting the time-dependent consumption of monomer to [AGE]/[AGE]0 = e–kapp × t or –ln[AGE]/[AGE]0 = kapp× t. The apparent rate constants (kapp [=] s–1) are compared for neat polymerizations of AGE with a targeted degree of polymerization of 87 (10,000 g/mol). Figure 1b shows a plot of the normalized monomer concentration as a function of time as measured by in-situ FTIR for an AGE polymerization utilizing (1). The apparent propagation rate constant for (1) (kapp(1)) was 4.8 × 10–3 s–1 ([(1)]0 = 97 mmol/L). Plots of monomer consumption over time for polymerizations utilizing compounds (2), (3), and (4) are also present on the plot for comparison. Significantly, (1) represented a ca. 170fold increase in polymerization rate over the first-reported MOD initiator, [(Bn)2NCH2CH2(µ2O)Al(Et)2∙Al(Et)3 (2). The increase in rate due to amine substitution alone represented an increase in kapp of 50-fold from the Bn2N-functional MOD (4) to the Me2N-functional-MOD (1). The conclusion from this rate increase is that the alkylamine affects the site of monomer

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coordination and enchainment at every propagation event, and not just the first monomer addition associated with initiation as was proposed in previous work.37,38

Figure 1. (a) (1): [(H3C)2NCH2CH2(µ2-O)Al(iBu)2∙Al(iBu)3]. (2) [(Bn)2NCH2CH2(µ2O)Al(Et)2∙Al(Et)3].36 (3): [(Bn)2NCH2CH2(µ2-O)Al(Me)2∙Al(Me)3].35 (4): [(Bn)2NCH2CH2(µ2O)Al(iBu)2∙Al(iBu)3].35 All ellipsoids shown at 50% probability and Bn = benzyl. (b) The rate of epoxide polymerization initiated with MOD complexes has increased incrementally from (2)–(4) as alkyl substitution on aluminum was changed. (1) represents a disproportionate increase in polymerization rate with a change in alkyl substitution on nitrogen. (1) concludes a polymerization of allyl glycidyl ether (AGE) in minutes. Solution polymerizations using (1) were disproportionately slower compared with the rapid neat polymerizations. While a neat polymerization concluded after 16 minutes (kapp = 4.8 × 10–3 s–1, [(1)]0 = 97 mM), solution polymerizations required two days for completion (kapp = 1.6 × 10– 5

s–1, [(1)]0 = 46 mM). In light of this apparent discrepancy, we attempted to determine the

dependence of the polymerization rate on MOD (1) concentration. We monitored a series of AGE polymerizations at several MOD concentrations using 1H NMR spectroscopy in d6-benzene

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under isothermal conditions. The polymerization rates were calculated using the linear portion of the initial monomer consumption, which for these polymerizations utilized over 12 hours of spectroscopic data resulting in a change in monomer conversion of up to ca. 3%. The results are shown in Figure 2. Notably, the rate of polymerization increased exponentially with concentration of (1). The heat released due to epoxide ring opening was first considered as a potential source for the unusual high dependence of rate on concentration of (1). However, under our reaction conditions only negligible heating of the polymerization reaction would occur (< 0.1 ºC). We interpreted the experimentally measured rate (v [=] mM/min) as a function of [(1)] by fitting the rate (5) to v = v0 (1 + eκ

[(1)]

)/2 where κ describes the rate increase per-unit-

concentration of [(1)] added to the system (κ [=] mM–1), and v0 is the rate of an uncatalyzed reaction (v0 [=] mM/min). This empirical description is consistent with (1) possessing the characteristics of both initiator and catalyst, which would serve as a speculative explanation for the apparent autocatalytic polymerization. Next, we explored the structural basis for the autocatalytic behavior of (1) giving rise to the unusual behavior in Figure 2.

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Figure 2. The initial polymerization rate was measured under isothermal conditions by 1H NMR spectroscopy in d6-benzene at room temperature with no more than 3% conversion of AGE monomer. An apparent exponential dependence of polymerization rate on [(1)] was observed: – d[AGE]/dt = v(t) = v0(1+eK×[(1)])/2 with v0 = 1.206±0.003×10–7 mM/min as the polymerization rate in the absence of any catalytic activity, and K = 0.420±0.002 mM–1 as the per-unitconcentration enhancement in rate due to catalytic activity.

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Figure 3. The proposed intermediate (5) was synthesized from Me2NCH2CH2OCH2CH2OH and triisobutylaluminum according to the standard MOD synthetic procedure. The proposed intermediate is a dimer of MODs with a dative N–Al bond between alkylamine and trialkylaluminum.

Identification of the polymerization intermediate. To gain mechanistic insight, we attempted the synthesis of an analog to the polymerization intermediate by the reaction between of 2-(2-(dimethylamino)ethoxy)ethanol and triisobutylaluminum. We posit that this combination of reagents provided a model for the nascent propagating species after a single monomer enchainment of epoxide to the MOD, with the caveat that our model intermediate was formed via a different route than the true polymerization intermediate. The structure of the resultant complex (5) obtained by X-ray crystallography is shown in Figure 3. Detailed crystallographic data (Tables S7–S12) and NMR spectroscopy can be found in SI (Figures S2 and S10). The symmetric structure of the resultant compound was unanticipated. In particular, (5) presented a

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bis(µ-alkoxo-dialkylaluminum) (BOD) structure. Complex (5) was a dimeric complex of the monomeric MOD as noted previously by Atwood et al. on related complexes.40 To substantiate if the purported intermediate (5) was representative of the polymerization intermediate, we first compared the rates of AGE polymerization using (1) and (5). Similar polymerization rates produced by (1) and (5) would support that the BOD structure (5) may indeed be representative of the polymerization intermediate formed by MODs (1)–(4). All neat polymerizations were performed in duplicate at 60 ºC. Aliquots of the active polymerizations were taken at time points of 5, 10, 15, 20, 25, 30, 45, and 60 minutes and conversion was determined by 1H NMR spectroscopy of the remaining unreacted monomer in the crude reaction mixture. Under these conditions, (1) and (5) produced a first-order consumption of AGE monomer with kapp(1) of 1.40 ± 0.02 × 10–4 s–1 for (1) and kapp(5) = 1.62 ± 0.02 × 10–4 s–1 for (5) as shown in Figure 4. The kinetic similarity between (1) and (5) under identical reaction conditions suggested that MODs (1)–(4) may dimerize into BOD structures as the active polymerization intermediate (Scheme 2).

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Figure 4. Comparison of polymerization rate using compounds (1) and (5). Apparent rate constants were determined by fitting –ln[AGE]/[AGE]0 = kapp × t: kapp(1) = 1.40 ± 0.02 × 10–4 s–1, kapp(5) = 1.60 ± 0.02 × 10–4 s–1 neat at 60 ºC. To obtain more direct evidence of a MOD to BOD transition, we utilized THF as a proxy monomer to observe MOD dimerization under similar conditions encountered in polymerization, but in the absence of chain-growth. THF was titrated in increasing amounts to (1) in d6-benzene and 1H NMR spectra were collected on the reaction mixtures. The 1H NMR spectra are shown in Figure 5. As the THF concentration was increased, new peaks appeared and grew proportionally to the decrease in peaks associated with (1). The positions of the new signals were similar to those observed from the proposed intermediate (5) in d6-benzene (Figure S2). The reduced number of signals was consistent with the more symmetric, dimeric structure. The signals associated with the diatopic protons due to the bend in the N–C–C–O–AlR3 plane of (1) converge into degenerate signals as THF was added, which was further consistent with symmetrization. 1

H-1H Correlated NMR Spectroscopy (COSY) was also performed on the sample with two

equivalents of THF. Interpretation of the COSY spectrum suggested that there were two species present in solution; one set of peaks was attributed to the dimerized structure (Figure S3) and a separate set of signals was associated with the MOD. Likewise, in epoxide polymerization we

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propose that exposure of the MOD to epoxide monomer removes the datively-bound AlR3 and provokes MOD dimerization while the liberated alkylamine captures the mobile AlR3 species. Details of the interpretations of the COSY spectrum can be found in the SI, Figure S3. Combined, the NMR spectroscopy data provides further evidence that monomer induces the MOD→BOD dimerization, where the BOD serves as the active polymerization intermediate in MOD initiated epoxide polymerization. While these results provide evidence for the structure of the active polymerization species, they do not yet explain the steep increase in rate we see with changes in amine substitution, and with increases in concentration of (1).

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Scheme 2. Proposed MOD to BOD transition to active polymerization intermediate.

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Figure 5. 1H NMR spectra of (1) in d6-benzene with increasing equivalents of THF added. From bottom to top: 0.00, 0.25, 0.5, 10, and 2.0 equivalents of THF. As the concentration of THF was increased, the peaks associated with the monomer species (1), highlighted in blue, decrease and new peaks, highlighted in red, grow which we attribute to the dimerized species. COSY spectra (Figures S3) further substantiate this interpretation. Integrals are indicated in black below peaks. Asterisks indicate reference integrals. Our previously proposed mechanism for MOD-initiated polymerization of epoxides was consistent with experimental kinetic observations on a homologous series of MOD initiators with variation in alkylaluminum substitution. The polymerization rate was proposed to be covariant with the bond length between the datively bound trialkylaluminum and aluminum-alkoxide R3Al–O,37 which was proposed to be the site of monomer enchainment. The current 170-fold enhancement in polymerization rate with a change in alkylamine substitution is inconsistent with our earlier mechanistic interpretation that presented the alkylamine as passive in the

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polymerization mechanism. The new results suggest an alternative hypothesis: The aluminoxane ring may be acting as initiator and the site of monomer enchainment (see Figure S4 for electrospray ionization mass spectrometry showing end group structure of a model poly(propylene oxide) synthesized for end-group determination), while the N-Al adduct, which forms upon MOD dimerization, may be acting as a catalyst as depicted in Figure 6. Merged initiation and catalytic functionalities would help explain the precipitous increase in polymerization rate with concentration of (1) shown in Figure 2. However, cooperativity is another possibility. To explore the possibility that the MODs were acting as both catalyst and initiator, we decoupled the proposed initiation and catalytic moieties into discrete species.

Figure 6. The distinct catalytic and initiation/propagation functionality of (1)–(5) was separated into distinct initiator (6) 41 and catalyst (7) species.

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Figure 7. A plot of –ln[AGE]/[AGE]0 as a function of time for AGE polymerizations utilized (6) (green squares), (7) (blue triangles) and combined (6) + (7) (red circles). The catalyst (7) alone did not produce polymer. Initiator (6) produced a slow polymerization. The polymerization rate increased precipitously when both initiator (6) and catalyst (7) were present.

Decoupling catalytic and chain-growth functionality with distinct N-Al adduct catalysts and aluminum alkoxide initiators. An independent initiating BOD (6) and N-Al adduct (7) were synthesized to decouple the catalytic site from the site of chain-growth. We synthesized a simple BOD structure (6) previously reported by Francis et al.41 in a similar manner to (5) via the reaction of methoxy-ethanol and trimethyl-aluminum, which we hypothesize would provide a site for monomer addition and end-group control. The structure of (6) was verified by X-ray crystallography and can be seen in Figure 6 with further structural details given in the SI (Figure S11, Tables S13–S18). The adduct of triethylamine and trimethylaluminum (7) was synthesized by reacting the aforementioned compounds in hexane at –78 ºC. These precursors were selected for synthetic convenience. The adduct was purified via crystallization. The structure of (7), determined by X-ray crystallography, is shown in Figure 6. Detailed structural information can be found in the SI (Figure S12, Tables S19–S24). The formation of analogously

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stable alkylaluminum-alkylamine N–Al adducts has been reported previously.42,43 Density functional theory calculations at the B3LYP/6-31++g(d,p) level of theory predict a N-Al bond dissociation energy of ca. –16 kcal/mol for (7). Details of the calculation are given in SI (Figure S13). In order to determine how these species contribute to epoxide polymerizations, we incubated (6), (7), and (6)+(7) with AGE monomer and monitored the consumption of monomer over time. Figure 7 shows a plot of –ln([AGE]/[AGE]0) as a function of time. The slope of the line corresponds to kapp for the polymerization. From these data, the N-Al adduct catalyst (7) by itself does not polymerize AGE, while the BOD (6) initiator slowly polymerizes AGE, consistent with our previous work (kapp(6) = 9.48±1.21 × 10–6 s–1). Significantly, in the presence of both (6) and (7), a significant increase in polymerization rate was observed. The enhanced rate was comparable to the performance of the structures (1) and (5) with kapp(6)+(7) = 1.78 ± 0.06 × 10–4 s– 1

. This decisive result supports the assignment of catalytic activity to the N-Al adduct, and the

site of chain growth to the aluminum alkoxide. Electrospray ionization mass spectrometry of a model poly(propylene oxide) synthesized for determination of end-group structure is shown in Figure S5, and is consistent with a methoxy-ethanol end-group derived from (6). A key advantage of decoupling the chain-growth and catalytic functionalities is the potential for orthogonal control over molecular weight and polymerization rate. In a series of duplicate AGE polymerizations targeting 10,000 g/mol, we increased the concentration of the N-Al adduct catalyst (7) to 1.0, 2.0, and 4.0 equivalents relative to (6) and observed a significant increase in polymerization rate (Figure 8). The apparent rate constants increased significantly with N-Al concentration: 0.0 eq. (7) kapp(6) = 9.48 ± 1.21 × 10–6 s–1, 1.0 eq. (7) kapp(6)+(7) = 1.78 ± 0.06 × 10–4 s–1, 2.0 eq. (7) kapp(6)+2(7) = 17.2 ± 0.12 × 10–4 s–1, and 4.0 eq. (7) kapp(6)+4(7) = 69.0 ± 10.5 × 10–4 s– 1

. Every added equivalent of (7) relative to initiator (6) produced an appreciable increase in kapp

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within the range of (7) concentrations explored. This result is reminiscent of the increase in polymerization rate seen with increasing concentration of (1) shown in Figure 2. The resultant molecular weights conformed closely to the targeted molecular weight of 10 000 g/mol PAGE: 1.0 eq. of (7) Mn = 9,300 g/mol, 2.0 eq. of (7) Mn = 8,100 g/mol, and 4.0 eq. of (7) Mn = 7,350 g/mol. The dispersities were respectively 1.34, 1.07, and 1.09. When we substituted the N-Al adduct (7) with trimethylaluminum, we observed a slower, non-living polymerization (Figure S6) that terminated at low conversion (ca. 35%). We speculate that the dynamic and aggregating nature of alkylaluminum species led to a gradual transformation of AlMe3 into a noncatalytic form during the polymerization. The persistence of the N-Al adduct (7) could be accounted for based on the increased stability of alkylaluminum species when coordinated by alkylamines.42,4449 1

H-1H COSY and NOESY experiments (Figures S7 and S8, respectively) were consistent with

the persistence of the N-Al adduct in solution.

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Figure 8. Unitless concentration of monomer [AGE]/[AGE]0 versus polymerization time for initiator (6) (black triangle), and increasing equivalents of N–Al adduct catalyst (7) relative to initiator (6): 1.0 eq. (7) (yellow diamonds), 2.0 eq. (7) (blue squares), and 4.0 eq. (7) (red circles). All polymerizations were performed in duplicate. The polymerization kinetics of the N-Al adduct (7) in the presence of the initiator were consistent with the trends observed for the compounds with tethered catalyst and initiator (1)– (5). All of the data exhibit a strong kinetic dependence on N-Al concentration, which suggests a consistent mechanism among (1)–(7). We speculate that the high dependence of rate on catalyst concentration is due to cooperativity among N-Al species. Future work will focus on elucidating detailed structure-kinetic relationships for the N-Al adduct catalysts, and the mechanistic basis for the high dependence of rate on catalyst concentration. Conclusion

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A new mono(µ-oxo)-dialuminum (MOD) initiator was synthesized, which provided a considerable increase in the rate of polymerization for allyl glycidyl ether compared to previously reported homologous initiators for epoxide polymerization. New mechanistic insight was gained through isolation of a bis(µ-oxo-dialkylaluminum) (BOD) polymerization intermediate, which was corroborated by detailed NMR spectroscopy experiments. The change in structure of MOD precursor to BOD intermediate in the presence of datively coordinating moieties (e.g., epoxide, THF) and the strong dependence of polymerization rate on MOD/BOD concentration suggested the coupled catalytic and enchainment functionalities of the MOD/BOD system. This was verified by decoupling the associated moieties into distinct chemical species, which led to the isolation of a trialkylaluminum-trialkylamine (N-Al) adduct as a stable and effective catalyst for the living polymerization of epoxides. The N-Al adduct exhibited a strong dependence of polymerization rate on concentration similar to the MOD/BOD system, which suggested a consistent mechanism. The MOD initiators and N-Al adduct catalysts are unique and effective tools for the general polymerization of functional epoxides that offer control of molecular weight of structurally diverse polyethers in a short period of time under simple reaction conditions. ASSOCIATED CONTENT Supporting Information. Materials and methods, as well as additional spectra, chromatograms, mass spectrograms, computational details, and crystallographic data can be found in supporting information. AUTHOR INFORMATION Corresponding Author

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*[email protected] Present Addresses ¶

Current affiliation: Department of Chemical Engineering and Materials Science, Michigan State

University, East Lansing, MI, USA. Funding Sources Welch Foundation (F-1904) National Science Foundation (DMR-1720595) National Institutes of Health (1 S10 OD021508-01) ACKNOWLEDGMENT The authors thank the Welch Foundation (F-1904) for support of this research. This research was partially supported by the National Science Foundation through the Center for Dynamics and Control of Materials: An NSF MRSEC under Cooperative Agreement No. DMR-1720595. The authors thank Dr. Vincent M. Lynch of the X-ray Diffraction Laboratory at the University of Texas at Austin in the Department of Chemistry. NMR spectra were collected on a Bruker Avance III 500 funded by the NIH (1 S10 OD021508-01). REFERENCES (1)

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